Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy

Wang, Dunyang Rita; Shah, Deep B.; Maslyn, Jacqueline A.; Loo, Whitney S.; Wujcik, Kevin H.; Nelson, Erik J.; Latimer, Matthew J.; Feng, Jun; Prendergast, David; Pascal, Tod A.; Balsara, Nitash P.

doi:10.1149/2.0981814jes

Title: Rate Constants of Electrochemical Reactions in a Lithium-Sulfur Cell Determined by Operando X-ray Absorption Spectroscopy

Journal Article · 08 November 2018 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/2.0981814jes · OSTI ID:1490458

Wang, Dunyang Rita ^[1];

^[1]; Maslyn, Jacqueline A. ^[1]; Loo, Whitney S. ^[2]; Wujcik, Kevin H. ^[1]; Nelson, Erik J. ^[3]; Latimer, Matthew J. ^[3]; Feng, Jun ^[4]; Prendergast, David ^[4]; Pascal, Tod A. ^[4];

^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The reduction of sulfur during discharge in a lithium-sulfur (Li-S) cell is known to occur in a series of reaction steps that involve lithium polysulfide intermediates. We present an operando study of the discharge of a solid-state Li-S cell using X-ray absorption spectroscopy (XAS). In theory, the average chain length of the polysulfides, x_avg,cell, at a given depth of discharge is determined by the number of electrons delivered to the sulfur cathode. The dependence of x_avg,cell measured by XAS on the depth of discharge is in excellent agreement with theoretical predictions. XAS is also used to track the formation of Li₂S, the final discharge product, as a function of depth of discharge. The XAS measurements were used to estimate rate constants of a series of simple reactions commonly accepted in literature.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1490458

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 14 Vol. 165; ISSN 0013-4651

Publisher:: IOP Publishing - The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

Anionic polymerization: High vacuum techniques Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18 https://doi.org/10.1002/1099-0518(20000915)38:18%3c3211::AID-POLA10%3e3.0.CO;2-L	journal	January 2000
Radical or Not Radical: Revisiting Lithium-Sulfur Electrochemistry in Nonaqueous Electrolytes Cuisinier, Marine; Hart, Connor; Balasubramanian, Mahalingam Advanced Energy Materials, Vol. 5, Issue 16 https://doi.org/10.1002/aenm.201401801	journal	January 2015
Lithium/Sulfur Batteries Upon Cycling: Structural Modifications and Species Quantification by In Situ and Operando X-Ray Diffraction Spectroscopy Waluś, Sylwia; Barchasz, Céline; Bouchet, Renaud Advanced Energy Materials, Vol. 5, Issue 16 https://doi.org/10.1002/aenm.201500165	journal	May 2015
Characterization of Polysulfide Radicals Present in an Ether-Based Electrolyte of a Lithium-Sulfur Battery During Initial Discharge Using In Situ X-Ray Absorption Spectroscopy Experiments and First-Principles Calculations Wujcik, Kevin H.; Pascal, Tod A.; Pemmaraju, C. D. Advanced Energy Materials, Vol. 5, Issue 16 https://doi.org/10.1002/aenm.201500285	journal	June 2015
Lithium-Sulfur Batteries: Electrochemistry, Materials, and Prospects Yin, Ya-Xia; Xin, Sen; Guo, Yu-Guo Angewandte Chemie International Edition, Vol. 52, Issue 50 https://doi.org/10.1002/anie.201304762	journal	November 2013
X-ray Absorption Near-Edge Structure and Nuclear Magnetic Resonance Study of the Lithium-Sulfur Battery and its Components Patel, Manu U. M.; Arčon, Iztok; Aquilanti, Giuliana ChemPhysChem, Vol. 15, Issue 5 https://doi.org/10.1002/cphc.201300972	journal	February 2014
Application of In Operando UV/Vis Spectroscopy in Lithium-Sulfur Batteries Patel, Manu U. M.; Dominko, Robert ChemSusChem, Vol. 7, Issue 8 https://doi.org/10.1002/cssc.201402215	journal	July 2014
The use of polymers in Li-S batteries: A review Dirlam, Philip T.; Glass, Richard S.; Char, Kookheon Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 10 https://doi.org/10.1002/pola.28551	journal	March 2017
In-situ X-ray diffraction studies of lithium–sulfur batteries Cañas, Natalia A.; Wolf, Steffen; Wagner, Norbert Journal of Power Sources, Vol. 226 https://doi.org/10.1016/j.jpowsour.2012.10.092	journal	March 2013
Transient existence of crystalline lithium disulfide Li2S2 in a lithium-sulfur battery Paolella, Andrea; Zhu, Wen; Marceau, Hugues Journal of Power Sources, Vol. 325 https://doi.org/10.1016/j.jpowsour.2016.06.086	journal	September 2016
Study of gas permeabilities through polystyrene-block-poly(ethylene oxide) copolymers Minelli, Matteo; Giacinti Baschetti, Marco; Hallinan, Daniel T. Journal of Membrane Science, Vol. 432 https://doi.org/10.1016/j.memsci.2012.12.038	journal	April 2013
Identification of lithium–sulfur battery discharge products through 6Li and 33S solid-state MAS and 7Li solution NMR spectroscopy Huff, Laura A.; Rapp, Jennifer L.; Baughman, Jessi A. Surface Science, Vol. 631 https://doi.org/10.1016/j.susc.2014.07.027	journal	January 2015
Lithium/Sulfur Cell Discharge Mechanism: An Original Approach for Intermediate Species Identification Barchasz, Céline; Molton, Florian; Duboc, Carole Analytical Chemistry, Vol. 84, Issue 9 https://doi.org/10.1021/ac2032244	journal	April 2012
Analytical Detection of Polysulfides in the Presence of Adsorption Additives by Operando X-ray Absorption Spectroscopy Dominko, Robert; Patel, Manu U. M.; Lapornik, Vida The Journal of Physical Chemistry C, Vol. 119, Issue 33 https://doi.org/10.1021/acs.jpcc.5b05609	journal	August 2015
Lithium Polysulfide Radical Anions in Ether-Based Solvents Wujcik, Kevin H.; Wang, Dunyang Rita; Raghunathan, Aditya The Journal of Physical Chemistry C, Vol. 120, Issue 33 https://doi.org/10.1021/acs.jpcc.6b04264	journal	August 2016
Structural Dependence of the Sulfur Reduction Mechanism in Carbon-Based Cathodes for Lithium–Sulfur Batteries Burgos, Juan C.; Balbuena, Perla B.; Montoya, Javier A. The Journal of Physical Chemistry C, Vol. 121, Issue 34 https://doi.org/10.1021/acs.jpcc.7b05554	journal	August 2017
Revealing Charge Transport Mechanisms in Li ₂ S ₂ for Li–Sulfur Batteries Liu, Zhixiao; Balbuena, Perla B.; Mukherjee, Partha P. The Journal of Physical Chemistry Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acs.jpclett.6b03063	journal	March 2017
Conductivity of Block Copolymer Electrolytes Containing Lithium Polysulfides Wang, Dunyang Rita; Wujcik, Kevin H.; Teran, Alexander A. Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/acs.macromol.5b00928	journal	July 2015
Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H. Nano Letters, Vol. 17, Issue 4 https://doi.org/10.1021/acs.nanolett.7b00249	journal	March 2017
Revealing the Electrochemical Charging Mechanism of Nanosized Li ₂ S by in Situ and Operando X-ray Absorption Spectroscopy Zhang, Liang; Sun, Dan; Feng, Jun Nano Letters, Vol. 17, Issue 8 https://doi.org/10.1021/acs.nanolett.7b02381	journal	July 2017
Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge Zheng, Dong; Liu, Dan; Harris, Joshua B. ACS Applied Materials & Interfaces, Vol. 9, Issue 5 https://doi.org/10.1021/acsami.6b08904	journal	September 2016
Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries Lee, Chang-Wook; Pang, Quan; Ha, Seungbum ACS Central Science, Vol. 3, Issue 6 https://doi.org/10.1021/acscentsci.7b00123	journal	May 2017
In Situ Raman Spectroscopy of Sulfur Speciation in Lithium–Sulfur Batteries Wu, Heng-Liang; Huff, Laura A.; Gewirth, Andrew A. ACS Applied Materials & Interfaces, Vol. 7, Issue 3 https://doi.org/10.1021/am5072942	journal	January 2015
Challenges and Prospects of Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300179v	journal	June 2012
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries Nelson, Johanna; Misra, Sumohan; Yang, Yuan Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja2121926	journal	March 2012
Ab Initio Structure Search and in Situ ⁷ Li NMR Studies of Discharge Products in the Li–S Battery System See, Kimberly A.; Leskes, Michal; Griffin, John M. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja508982p	journal	November 2014
Effects of Liquid Electrolytes on the Charge–Discharge Performance of Rechargeable Lithium/Sulfur Batteries: Electrochemical and in-Situ X-ray Absorption Spectroscopic Studies Gao, Jie; Lowe, Michael A.; Kiya, Yasuyuki The Journal of Physical Chemistry C, Vol. 115, Issue 50, p. 25132-25137 https://doi.org/10.1021/jp207714c	journal	October 2011
Probing the Lithium–Sulfur Redox Reactions: A Rotating-Ring Disk Electrode Study Lu, Yi-Chun; He, Qi; Gasteiger, Hubert A. The Journal of Physical Chemistry C, Vol. 118, Issue 11 https://doi.org/10.1021/jp500382s	journal	March 2014
Experimental and Theoretical Analysis of Products and Reaction Intermediates of Lithium–Sulfur Batteries Cañas, Natalia A.; Fronczek, David N.; Wagner, Norbert The Journal of Physical Chemistry C, Vol. 118, Issue 23 https://doi.org/10.1021/jp5013208	journal	May 2014
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401763d	journal	September 2013
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan The Journal of Physical Chemistry Letters, Vol. 5, Issue 9 https://doi.org/10.1021/jz500260s	journal	April 2014
Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita Nature Energy, Vol. 2, Issue 6 https://doi.org/10.1038/nenergy.2017.69	journal	May 2017
Erratum: Li–O2 and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3237	journal	December 2011
Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries Cuisinier, M.; Cabelguen, P. -E.; Adams, B. D. Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00372A	journal	January 2014
Lithium sulfur batteries, a mechanistic review Wild, M.; O'Neill, L.; Zhang, T. Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE01388G	journal	January 2015
Insight into the role of Li ₂ S ₂ in Li–S batteries: a first-principles study Yang, Guochun; Shi, Shaoqing; Yang, Jinghai Journal of Materials Chemistry A, Vol. 3, Issue 16 https://doi.org/10.1039/C5TA00499C	journal	January 2015
Investigation of the reaction mechanism of lithium sulfur batteries in different electrolyte systems by in situ Raman spectroscopy and in situ X-ray diffraction Zhu, W.; Paolella, A.; Kim, C. -S. Sustainable Energy & Fuels, Vol. 1, Issue 4 https://doi.org/10.1039/C6SE00104A	journal	January 2017
Advances in Li–S batteries Ji, Xiulei; Nazar, Linda F. Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826 https://doi.org/10.1039/b925751a	journal	January 2010
New insight into the working mechanism of lithium–sulfur batteries: in situ and operando X-ray diffraction characterization Waluś, Sylwia; Barchasz, Céline; Colin, Jean-François Chemical Communications, Vol. 49, Issue 72 https://doi.org/10.1039/c3cc43766c	journal	January 2013
Electrochemical reactions of lithium–sulfur batteries: an analytical study using the organic conversion technique Kawase, Ayako; Shirai, Soichi; Yamoto, Yoshinari Phys. Chem. Chem. Phys., Vol. 16, Issue 20 https://doi.org/10.1039/c4cp00958d	journal	January 2014
Mechanistic insights into operational lithium–sulfur batteries by in situ X-ray diffraction and absorption spectroscopy Lowe, Michael A.; Gao, Jie; Abruña, Héctor D. RSC Advances, Vol. 4, Issue 35 https://doi.org/10.1039/c4ra01388c	journal	January 2014
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
Rechargeable Lithium Sulfur Battery Cheon, Sang-Eun; Ko, Ki-Seok; Cho, Ji-Hoon Journal of The Electrochemical Society, Vol. 150, Issue 6 https://doi.org/10.1149/1.1571532	journal	January 2003
Rechargeable Lithium Sulfur Battery Cheon, Sang-Eun; Ko, Ki-Seok; Cho, Ji-Hoon Journal of The Electrochemical Society, Vol. 150, Issue 6, p. A800-A805 https://doi.org/10.1149/1.1571533	journal	May 2003
Time-Resolved In Situ Spectroelectrochemical Study on Reduction of Sulfur in N,N[sup ʹ]-Dimethylformamide Han, Dong-Hun; Kim, Bum-Soo; Choi, Shin-Jung Journal of The Electrochemical Society, Vol. 151, Issue 9 https://doi.org/10.1149/1.1773733	journal	January 2004
Polysulfide Shuttle Study in the Li/S Battery System Mikhaylik, Yuriy V.; Akridge, James R. Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976 https://doi.org/10.1149/1.1806394	journal	January 2004
Lithium Sulfur Battery: Oxidation/Reduction Mechanisms of Polysulfides in THF Solutions Yamin, H.; Gorenshtein, A.; Penciner, J. Journal of The Electrochemical Society, Vol. 135, Issue 5, p. 1045-1048 https://doi.org/10.1149/1.2095868	journal	January 1988
A Lithium/Dissolved Sulfur Battery with an Organic Electrolyte Rauh, R. D. Journal of The Electrochemical Society, Vol. 126, Issue 4 https://doi.org/10.1149/1.2129079	journal	January 1979
Operando Characterization of Intermediates Produced in a Lithium-Sulfur Battery Gorlin, Yelena; Siebel, Armin; Piana, Michele Journal of The Electrochemical Society, Vol. 162, Issue 7 https://doi.org/10.1149/2.0081507jes	journal	January 2015
Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries Miller, Elizabeth C.; Kasse, Robert M.; Heath, Khloe N. Journal of The Electrochemical Society, Vol. 165, Issue 1 https://doi.org/10.1149/2.0091801jes	journal	June 2017
In-Situ Raman Investigation of Polysulfide Formation in Li-S Cells Hagen, M.; Schiffels, P.; Hammer, M. Journal of The Electrochemical Society, Vol. 160, Issue 8 https://doi.org/10.1149/2.045308jes	journal	January 2013
Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy Gorlin, Yelena; Patel, Manu U. M.; Freiberg, Anna Journal of The Electrochemical Society, Vol. 163, Issue 6 https://doi.org/10.1149/2.0631606jes	journal	January 2016
Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries Wang, Qiang; Zheng, Jianming; Walter, Eric Journal of The Electrochemical Society, Vol. 162, Issue 3 https://doi.org/10.1149/2.0851503jes	journal	December 2014
In Situ X-ray Absorption Spectroscopy Studies of Discharge Reactions in a Thick Cathode of a Lithium Sulfur Battery Wujcik, Kevin H.; Wang, Dunyang Rita; Pascal, Tod A. Journal of The Electrochemical Society, Vol. 164, Issue 2 https://doi.org/10.1149/2.1441614jes	journal	December 2016
In-Situ Raman Spectroscopy of Sulfur Speciation in Lithium-Sulfur Batteries Wu, Heng-Liang; Huff, Laura A.; Gewirth, Andrew A. ECS Meeting Abstracts, Vol. MA2015-01, Issue 2, p. 249-249 https://doi.org/10.1149/ma2015-01/2/249	journal	April 2015
Polymer electrolytes: Fundamentals and applications Sequeira, César; Santos, Diogo https://doi.org/10.1533/9781845699772	book	December 2009

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